Fluoropolymer compositions and treated substrates

ABSTRACT

A polymer having at least one carbamate linkage prepared by: (i) reacting (a) at least one diisocyanate, polyisocyanate, or mixture thereof, and (b) at least one fluorinated compound selected from the formula (I): 
       R f (CH 2 ) x [(CF 2 CF 2 ) y (CH 2 CH 2 ) z ] m (R 1 ) r —XH   (I) 
     wherein 
     R f  is a perfluoroalkyl group having 1 to about 6 carbon atoms; 
     subscript x is 1 to about 6; 
     subscripts y, z and m are each independently 1, 2 or 3, or a mixture thereof; 
     subscript r is 0 or 1; 
     the total number of carbons in said formula (I) excluding (R 1 ) r —XH ranges from about 8 to about 22; 
     X is —O—, —NR—, —S—, —S(CH 2 ) t O—, or —S(CH 2 ) t NR—; 
     subscript t is from 1 to about 10; 
     R is H or C 1-4  alkyl; 
     R 1  is certain divalent radicals; 
     n is 2 to 4; 
     s is 1 to about 50; 
     R 2 , R 3 , and R 4  are each independently hydrogen or a C 1 -C 6  alkyl group; and 
     (ii) optionally reacting with (c) water, a linking agent, or a mixture thereof.

FIELD OF THE INVENTION

The present invention relates to the use of fluoropolymers containing acarbamate linkage to provide surface effects to substrates.

BACKGROUND OF THE INVENTION

Various compositions are known to be useful as treating agents toprovide surface effects to substrates. Surface effects includerepellency to moisture, soil, and stains, and other effects, which areparticularly useful for fibrous substrates and other substrates such ashard surfaces. Many such treating agents are fluorinated polymers orcopolymers.

U.S. Pat. No. 5,411,766 discloses polyfluoro nitrogen containing organiccompounds useful to provide oil repellency, water repellency, soilresistance and/or soil release properties to substrates treatedtherewith. Compounds exemplified contain mixtures of perfluoroalkylgroups having predominantly eight or more carbons.

Customer requirements for surface protection products are in a state ofconstant evolution, and there is a continuing need for newcost-effective, environmentally friendly chemical intermediates andproducts. Industry is constantly searching for compounds with minimumenvironmental impact and higher fluorine efficiency. In particular thereis a need for short chain fluorochemicals wherein some of the expensivefluorocarbon moieties have been replaced with less expensive and morereadily biodegradable moieties. However, the performance must bemaintained or superior despite the reduction in fluorine. The presentinvention provides such fluorochemicals.

SUMMARY OF INVENTION

The present invention comprises a polymer having at least one carbamatelinkage prepared by: (i) reacting (a) at least one diisocyanate,polyisocyanate, or mixture thereof, having isocyanate groups, and (b) atleast one fluorinated compound selected from the formula (I):

R_(f)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)(R¹)_(r)—XH   (I)

wherein

R_(f) is a linear or branched chain perfluoroalkyl group having 1 toabout 6 carbon atoms;

subscript x is an integer from 1 to about 6;

subscripts y, z and m are each independently 1, 2 or 3, or a mixturethereof;

subscript r is 0 or 1;

the total number of carbons in said formula (I) excluding (R¹)_(r)—XHranges from about 8 to about 22;

X is —O—, —NR—, —S—, —S(CH₂)_(t)O—, or —S(CH₂)_(t)NR—;

subscript t is from 1 to about 10;

R═H or C₁₋₄alkyl;

R¹ is a divalent radical selected from the group consisting of—S(CH₂)_(n)—,

n is an integer of 2 to 4;

s is an integer of 1 to 50;

R², R³, and R⁴ are each independently hydrogen or an alkyl groupcontaining 1 to 6 carbon atoms; and

-   -   (ii) optionally reacting with (c) water, a linking agent, or a        mixture thereof.

The present invention further comprises a method of providing waterrepellency, oil repellency, soil resistance, hydrophilic stain release,and wicking to substrates comprising contacting said substrate with apolymer having at least one carbamate linkage prepared by: (i) reacting(a) at least one diisocyanate, polyisocyanate, or mixture thereof,having isocyanate groups, and (b) at least one fluorinated compoundselected from the formula (I) as disclosed above; and (ii) reacting with(c) water, a linking agent, or a mixture thereof.

The present invention further comprises a substrate to which has beenapplied a polymer having at least one carbamate linkage prepared by: (i)reacting (a) at least one diisocyanate, polyisocyanate, or mixturethereof, having isocyanate groups, and (b) at least one fluorinatedcompound selected from the formula (I), as disclosed above, and (ii)reacting with (c) water, a linking agent, or a mixture thereof.

DETAILED DESCRIPTION OF INVENTION

Hereinafter trademarks are designated by upper case.

The present invention comprises a polymer having at least one carbamatelinkage prepared by: (i) reacting (a) at least one diisocyanate,polyisocyanate, or mixture thereof, having isocyanate groups, and (b) atleast one fluorinated compound selected from the formula (I):

R_(f)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)(R¹)_(r)—XH   (I)

wherein

R_(f) is a linear or branched chain perfluoroalkyl group having 1 toabout 6 carbon atoms;

subscript x is an integer from 1 to about 6;

subscripts y, z and m are each independently 1, 2 or 3, or a mixturethereof;

subscript r is 0 or 1;

the total number of carbons in said formula (I) excluding (R¹)_(r)—XHranges from about 8 to about 22;

X is —O—, —NR—, —S—, —S(CH₂)_(t)O—, or —S(CH₂)_(t)NR—;

subscript t is from 1 to about 10;

R is H or C₁₋₄ alkyl;

R¹ is a divalent radical selected from the group consisting of—S(CH₂)_(n)—,

n is an integer of 2 to 4;

s is an integer of 1 to 50;

R², R³, and R⁴ are each independently hydrogen or an alkyl groupcontaining 1 to 6 carbon atoms; and

-   -   (ii) optionally reacting with (c) water, a linking agent, or a        mixture thereof.

Preferred embodiments are polymers wherein for the reactant of formula(I), X is O, subscript x is 1 or 2, subscript y is 1 or 2, subscript zis 1 or 2, subscript m is 1 or 2, and subscript r is zero. Otherpreferred embodiments are when R_(f) is a perfluoroalkyl having 4 to 6carbon atoms. Fluorinated compounds useful in various embodiments of theinvention are available by oligomerization of fluoroalkyl iodides by amixture of tetrafluoroethylene and ethylene to produce fluorinatedoligomeric ethylene-tetrafluoroethylene iodides. The iodides are used toprepare alkanols and other derivatives, which are useful as the reactantof formula (I) to prepare the polymers of the present invention. Theintermediate iodides and derivatives are represented by formula (II)

C_(n)F_(2n+1)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)(R¹)_(r)G   (II)

wherein

G is I, OH, SH, NH₂, NHR, S(CH₂)_(t)OH, or S(CH₂)_(t)NHR,

subscript n is an integer from 1 to about 6,

subscript x is an integer from 1 to about 6,

subscripts y, z and m are each independently 1, 2 or 3, or a mixturethereof,

subscript t is from 1 to about 10,

R, R¹ and subscript r are as defined in formula (I), and

the total number of carbons in said formula (II) excluding (R¹)_(r)Granges from about 8 to about 22.

The initial product of the oligomerization reaction is a mixture ofclosely related oligomers of formula (II) wherein G is iodide. Inaddition to the major resulting oligomer, there will be other oligomerswith slightly longer or shorter chain lengths, as is the nature of suchreactions. There will also be a small percentage of oligomers where theethylene and tetrafluoroethylene depart from the expected alternatingsequence. The above formula (II) is intended to comprise not only theoriginal mixture of oligomers from the oligomerization reaction and itsalcohol and (meth)acrylate derivatives, but also a purified or partiallypurified form of these mixtures, as well the individual components ofeach mixture.

If desired, the major chemicals in the reaction mixture can be separatedinto individual components by differences in solubilities, meltingpoints, vapor pressures and other features. For example, it has beenfound that the relative solubilities of such components in acetonitrileand tetrahydrofuran are useful in such purifications, as shown in theexamples which follow. Other solvents and methods can also be used, asreadily determined by those skilled in the art.

From a practical viewpoint, anything beyond the most simple purificationis likely to be an unnecessary expense. When the intermediates offormula (II) are converted into the compounds of formula (I), all of theoligomers of formula (II) are expected to show similar properties to themajor oligomer present, and be useful additions to the product offormula (I).

The fluoroalkyl iodides useful as telogen reactants for the preparationof the iodide compounds of formula (II) include C_(n)F_(2n+1)CH₂CH₂I,C_(n)F_(2n+1)CH₂I and C_(n)F_(2n+1)I, wherein n is an integer from 1 toabout 6. Preferably n is from about 2 to about 4; more preferably n is2. The most preferable fluoroalkyl iodide reactant isperfluoroethylethyl iodide.

The iodides of formula (II),

C_(n)F_(2n+1)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)I,

wherein m, n, x, y, and z are as defined above, are preferably preparedby oligomerization of C_(n)F_(2n+1)C₂H₄I, C_(n)F_(2n+1)CH₂I orC_(n)F₂₊₁I using a mixture of ethylene (ET) and tetrafluoroethylene(TFE). The reaction can be conducted at any temperature from roomtemperature to about 150° C. with a suitable radical initiator.Preferably the reaction is conducted at a temperature of from about 40°to about 100° C. with an initiator which has about a 10 hour half-lifein that range. The feed ratio of the starting materials in the gasphase, that is the moles of C_(n)F_(2n+1)C₂H₄I, C_(n)F_(2n+1)CH₂I orC_(n)F_(2n+1)I vs the combined moles of ethylene andtetrafluoroethylene, can be used to control conversion of the reaction.This mole ratio is from about 1:3 to about 20:1, preferably from about1:2 to a bout 5:1 The mole ratio of ethylene to tetrafluoroethylene isfrom about 1:10 to about 10:1, preferably from about 3:7 to about 7:3,and more preferably from about 4:6 to about 6:4.

The alcohols of formula (II)

C_(n)F_(2n+1)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)OH,

wherein m, n, x, y, and z are as described above, are prepared from theabove oligomeric iodides (C_(n)F_(2n+1)C₂H₄I, C_(n)F_(2n+1)CH₂I orC_(n)F_(2n+1)) using an oleum treatment and hydrolysis. It has beenfound, for example, that reacting with oleum (15% SO₃) at about 60° C.for about 1.5 hours, followed by hydrolysis using an iced dilute K₂SO₃solution, and then followed by heating to about 100° C. for about 30minutes gives satisfactory results. But other reaction conditions canalso be used. After being cooled to ambient room temperature, a solid isprecipitated, ioslated and purified. For example, the liquid is thendecanted and the solid is dissolved in ether and washed with watersaturated with NaCl, dried over anhydrous Na₂SO₄, and concentrated anddried under vacuum. Other conventional purification procedures can beemployed.

Alternatively, the alcohols of formula (II) can be prepared by heatingthe above oligomeric iodides (C_(n)F_(2n+1)C₂H₄I, C_(n)F_(2n+1)CH₂I orC_(n)F_(2n+1)I) with N-methylformamide to about 150° C. and holding forabout 19 hours. The reaction mixture is washed with water to give aresidue. A mixture of this residue with ethanol and concentratedhydrochloric acid is gently refluxed (at about 85° C. bath temperature)for about 2.5 hours. The reaction mixture is washed with water, dilutedwith dichloromethane, and dried over sodium sulfate. The dichloromethanesolution is concentrated and distilled at reduced pressure to give thealcohol. Optionally N,N dimethylformamide can be used instead ofN-methylformamide. Other conventional purification procedures can alsobe employed.

The amines of formula (II) ofC_(n)F_(2n+1)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)NH₂, wherein m, n,x, y, and z are as described above, are prepared from the oligomericazides (C_(n)F_(2n+1)C₂H₄I, C_(n)F_(2n+1)CH₂N₃ described below or fromC_(n)F_(2n+1)I) by reduction using hydrazine hydrate and Ni-Raney as pera modified literature procedure (Trabelsi, H.; Szoenyi, F.;Michelangeli, N.; Cambon, A., J. Fluorine Chem., 1994, 69,115-117).

Transformation of oligomer azide to amine was performed in a mixedsolvent system comprising 1:1 water and ethanol using hydrazinehydrate/Ni-Raney at 60 ° for 12 h. Alternatively, catalytichydrogenation using Pt/C or various conditions involving other reducingagents described also could be used to effect this transformation.

The azides of C_(n)F_(2n+1)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)N₃,wherein m, n, x, y, and z are as described above in formula (II), areprepared from the oligomeric iodides (C_(n)F_(2n+1)C₂H₄I,C_(n)F_(2n+1)CH₂I or C_(n)F_(2n+1)I) using sodium azide as per amodified procedure disclosed in the literature (Rondestvedt, C. S., Jr.;Thayer, G. L., Jr. J. Org. Chem. 1977, 42, 2680). Displacement of iodideto azide was performed in quantitative yields in a mixed solvent systemcomprising acetonitrile and water in a 3:1 ratio using sodium azide at90° C. Alternatively a solvent system comprising dimethylformamide-wateror acetone-water or isopropyl alcohol/water or other similar solventsystem can be used for this reaction under similar conditions. Phasetransfer reaction described by Cambon et. al. can be used for thisconversion, which produced only moderate yield (20-30%) of the azideafter 36 h at 100° C. (Trabelsi, H.; Szoenyi, F.; Michelangeli, N.;Cambon, A., J. Fluorine Chem., 1994, 69,115-117).

The thiols of formula (II) ofC_(n)F_(2n+1)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)SH wherein m, n, x,y, and z are as described above, are prepared from the oligomericiodides (C_(n)F_(2n+1)C₂H₄I, C_(n)F_(2n+1)CH₂I or C_(n)F_(2n+1)I) by thereaction with thiourea followed by hydrolysis of the thiouronium salt asper the literature procedure (Rondestvedt, C. S., Jr.; Thayer, G. L.,Jr. J. Org. Chem. 1977, 42, 2680). The oligomeric iodides were refluxedwith thiourea in ethanol for 36 h and hydrolyzed using sodium hydroxideto obtain the corresponding oligomeric thiols. Alternatively,displacement reaction using NaSH in ethanol could be used to effect thistransformation.

The sulfur-containing alcohols of formula (I) of the present inventionC_(n)F_(2n+1)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)S(CH₂)_(t)OH,wherein m, n, x, y, and z are as described above and r is 1 to 5, areprepared from the oligomeric iodides (Formula (I) where G is an iodide)by the displacement reaction with 2-mercaptoethanol as per theliterature procedure (Rondestvedt, C. S., Jr.; Thayer, G. L., Jr. J.Org. Chem. 1977, 42, 2680). The oligomeric iodides were refluxed with2-mercaptoethanol and sodium hydroxide in tert-butanol for 12 h toobtain the corresponding oligomeric hydroxyethyl sulfide.

The sulfur-containing amines of formula (I) of the present inventionC_(n)F_(2n+1)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)S(CH₂)_(t)NH₂,wherein m, n, x, y, and z are as described above and r is 1 to 5, areprepared from the oligomeric iodides (Formula (I) where G is an iodide)by the displacement reaction with 2-aminoethanethiol as per theliterature procedure. (Rondestvedt, C. S., Jr.; Thayer, G. L., Jr. J.Org. Chem. 1977, 42, 2680). The oligomeric iodides were refluxed with2-mercaptoethylamine hydrochloride and sodium hydroxide in tert-butanolfor 12 h to obtain the corresponding oligomeric aminoethyl sulfide.

Specific fluorinated alcohols of formula (II) useful in the preparationof the reactant of formula (I) are listed in Table 1A. The groups C₃F₇,C₄F₉, and C₆F₁₃, referred to in the list of specific alcohols in Tables1A refer to linear perfluoroalkyl groups unless specifically indicatedotherwise.

TABLE 1A Compound No. Structure 1. C₂F₅CH₂CH₂CF₂CF₂CH₂CH₂OH, 2.C₂F₅CH₂CH₂(CF₂CF₂)₂CH₂CH₂OH, 3. C₂F₅(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH, 4.C₂F₅CH₂CH₂CF₂CF₂(CH₂CH₂)₂OH, 5. C₂F₅CH₂CH₂(CF₂CF₂CH₂CH₂)₂OH, 6.C₂F₅(CH₂CH₂)₂(CF₂CF₂CH₂CH₂)₂OH, 7. C₂F₅(CH₂CH₂CF₂CF₂)₂(CH₂CH₂)₂OH 8.C₂F₅CH₂CH₂(CF₂CF₂)₃CH₂CH₂OH, 9. C₂F₅CH₂CH₂CF₂CF₂(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH,10. C₂F₅(CH₂CH₂)₂(CF₂CF₂)₂CH₂CH₂OH, 11. C₄F₉CH₂CH₂CF₂CF₂CH₂CH₂OH, 12.C₄F₉CH₂CH₂(CF₂CF₂)₂CH₂CH₂OH, 13. C₄F₉(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH, 14.C₄F₉CH₂CH₂CF₂CF₂(CH₂CH₂)₂OH, 15. C₄F₉CH₂CH₂(CF₂CF₂CH₂CH₂)₂OH, 16.C₄F₉(CH₂CH₂)₂(CF₂CF₂CH₂CH₂)₂OH, 17. C₄F₉(CH₂CH₂CF₂CF₂)₂(CH₂CH₂)₂OH 18.C₄F₉CH₂CH₂(CF₂CF₂)₃CH₂CH₂OH, 19.C₄F₉CH₂CH₂CF₂CF₂(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH, 20.C₄F₉(CH₂CH₂)₂(CF₂CF₂)₂CH₂CH₂OH, 21. C₆F₁₃CH₂CH₂CF₂CF₂CH₂CH₂OH, 22.C₆F₁₃CH₂CH₂(CF₂CF₂)₂CH₂CH₂OH, 23. C₆F₁₃(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH, 24.C₆F₁₃CH₂CH₂CF₂CF₂(CH₂CH₂)₂OH, 25. C₆F₁₃CH₂CH₂(CF₂CF₂CH₂CH₂)₂OH, 26.C₆F₁₃(CH₂CH₂)₂(CF₂CF₂CH₂CH₂)₂OH, 27. C₆F₁₃(CH₂CH₂CF₂CF₂)₂(CH₂CH₂)₂OH 28.C₆F₁₃CH₂CH₂(CF₂CF₂)₃CH₂CH₂OH, 29.C₆F₁₃CH₂CH₂CF₂CF₂(CH₂CH₂)₂CF₂CF₂CH₂CH₂OH, 30.C₆F₁₃(CH₂CH₂)₂(CF₂CF₂)₂CH₂CH₂OH.

Specific fluorinated telomer thiols of formula (II) wherein G is SH,which correspond to the above listed compounds 1 to 30 wherein G is OH,are also useful in the present invention to prepare the reactant offormula (I). Specific fluorinated telomer amines of formula (II) whereinG is NH₂, which correspond to the above listed compounds 1 to 30 whereinG is OH, are also useful in the present invention to prepare thereactant of formula (I).

The intermediates of formula (II) wherein G is OH, SH or NH₂ are used toprepare the reactant of formula (I) which is used to prepare thepolymers of the present invention. To make the fluoropolymers of thepresent invention, a compound of formula (I) is reacted with apolyisocyanate. The polyisocyanate reactant adds to the branched natureof the polymer. By the term “polyisocyanate” is meant di- and higherisocyanates and the term includes oligomers. Any polyisocyanate havingpredominately two or more isocyanate groups, or any isocyanate precursorof a polyisocyanate having predominately two or more isocyanate groups,is suitable for use in this invention. For example, hexamethylenediisocyanate homopolymers are suitable for use herein and arecommercially available. It is recognized that minor amounts ofdiisocyanates may remain in products having multiple isocyanate groups.An example of this is a biuret containing residual small amounts ofhexamethylene diisocyanate.

Also suitable for use as the polyisocyanate reactant are hydrocarbondiisocyanate-derived isocyanurate trimers. Preferred is DESMODUR N-3300(a hexamethylene diisocyanate-based isocyanurate available from BayerCorporation, Pittsburgh, Pa.). Other triisocyanates useful for thepurposes of this invention are those obtained by reacting three moles oftoluene diisocyanate with 1,1,1-tris-(hydroxymethyl)ethane or 1,1,1-tris(hydroxymethyl)propane. The isocyanurate trimer of toluene diisocyanateand that of 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate areother examples of triisocyanates useful for the purposes of thisinvention, as is methane-tris-(phenylisocyanate). Precursors ofpolyisocyanate, such as diisocyanate, are also suitable for use in thepresent invention as substrates for the polyisocyanates. DESMODURN-3600, DESMODUR Z4470, and DESMODUR XP 2410, from Bayer Corporation,Pittsburgh, Pa., and bis-(4-isocyanatocylohexyl)methane are alsosuitable in the invention.

Preferred polyisocyanate reactants are the aliphatic and aromaticpolyisocyanates containing biuret structures, or polydimethyl siloxanecontaining isocyanates. Such polyisocyanates can also contain bothaliphatic and aromatic substituents.

Particularly preferred as the polyisocyanate reactant for all theembodiments of the invention herein are hexamethylene diisocyanatehomopolymers commercially available, for instance as DESMODUR N-100,DESMODUR N-75 and DESMODUR N-3200 from Bayer Corporation, Pittsburgh,Pa.; 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate available,for instance as DESMODUR I (Bayer Corporation);bis-(4-isocyanatocylohexyl)methane available, for instance as DESMODUR W(Bayer Corporation) and diisocyanate trimers of formulas (IIa), (IIb),(IIc) and (IId):

The diisocyanate trimers (IIa-d) are available, for instance as DESMODURZ4470, DESMODUR IL, DESMODUR N-3300, and DESMODUR XP2410, respectively,from Bayer Corporation.

To make the fluoropolymers of the present invention, a compound offormula (I) is reacted with a polyisocyanate to produce a fluoropolymer.The fluoropolymer is typically prepared by charging a reaction vesselwith the polyisocyanate, the above fluoroalcohol, fluorothiol orfluoroamine, or mixture thereof, and optionally a non-fluorinatedorganic compound. The order of reagent addition is not critical. Thespecific weight of the polyisocyanate and other reactants charged isbased on their equivalent weights and on the working capacity of thereaction vessel, and is adjusted so that alcohol, thiol or amine, willbe consumed in the first step. The charge is agitated and temperatureadjusted to about 40° C.-70° C. Typically a catalyst such as a titaniumchelate in an organic solvent is then added and the temperature israised to about 80° C.-100° C. After holding for several hours,additional solvent and water, a linking agent, or a combination thereof,is added, and the mixture allowed to react for several more hours oruntil all of the isocyanate has been reacted. More water can then beadded along with surfactants, if desired, and stirred until thoroughlymixed. Following homogenization, the organic solvent can be removed byevaporation at reduced pressure, and the remaining aqueous solution ofthe fluoropolymer used as is or subjected to further processing.

In a preferred embodiment, step (i) reacting, further comprises (d) anon-fluorinated organic compound selected from the group consisting offormula

R₁₀—(R¹¹)_(k)—YH,

wherein

R¹⁰ is a linear, branched or cyclic C₁-C₁₈ alkyl, a C₁-C₁₈ omega-alkenylradical or a C₁-C₁₈omega-alkenoyl radical;

R¹¹ is

wherein

R², R³ and R⁴ are, independently, H or C₁ to C₆ alkyl;

s is 1 to 50;

k is 0 or 1; and

Y is —O—, —S—, or —N(R⁵)— wherein R⁵ is H or alkyl containing 1 to 6carbon atoms.

Preferably the non-fluorinated compound of formula R¹⁰—(R¹¹)_(k)—YHreacts with about 0.1 mol % to about 60 mol % of said isocyanate groups.

In another preferred embodiment, the compound of formulaR¹⁰—(R¹¹)_(k)—YH comprises a hydrophilic water-solvatable materialcomprising at least one hydroxyl-terminated polyether of formula (III):

wherein

R is a monovalent hydrocarbon radical containing no more than sixaliphatic or alicyclic carbon atoms;

Subscripts m and m2 are independently an average number of repeatingoxyethylene groups, and ml is an average number of repeatingoxypropylene groups, respectively; provided that m is always a positiveinteger, while m1 and m2 are a positive integer or zero. When m1 and m2are zero, formula (III) designates an oxyethylene homopolymer. When m1is a positive integer and m2 is zero, formula (III) designates a blockor random copolymer of oxyethylene and oxypropylene. When m1 and m2 arepositive integers, formula (III) designates a triblock copolymerdesignated PEG-PPG-PEG (polyethylene glycol-polypropyleneglycol-polyethylene glycol) More preferably, the hydrophilic,water-solvatable components (3) are the commercially availablemethoxypolyethylene glycols (MPEG's), or mixtures thereof, having anaverage molecular weight equal to or greater than about 200, and mostpreferably between 350 and 2000. Also commercially available, andsuitable for the preparation of the polyfluoro organic compounds of thepresent invention, are butoxypolyoxyalkylenes containing equal amountsby weight of oxyethylene and oxypropylene groups (Union Carbide Corp.50-HB Series UCON Fluids and Lubricants) and having an average molecularweight greater than about 1000.

The non-fluorinated compound of formula R¹⁰—(R¹¹)_(k)—YH is reacted instep (i) with the polyisocyanate and fluorinated compound of formula (I)as described above, prior to the reaction with water, linkage agent, ora mixture thereof. This initial reaction is conducted so that less than100% of the polyisocyanate groups are reacted. Following the initialreaction, water, linkage agent, or a mixture thereof, is added. Thereaction of water or linkage agent with the residual NCO groupscompletely reacts all of the isocyanate groups and eliminates a furtherpurification step that would be needed if other reactants were used at aratio sufficient to react with 100% of the isocyanate groups. Further,this addition greatly increases the molecular weight of the polymers andassures proper mixing if more than one reactant is used in the firststep of the polymer preparation, i.e., if a water solvatable componentis added, it is likely that at least one unit will be present in eachpolymer.

Linking agents useful in forming polymers of the invention organiccompounds have two or more Zerewitinoff hydrogen atoms (Zerevitinov,Th., Quantitative Determination of the Active Hydrogen in OrganicCompounds, Berichte der Deutschen Chemischen Gesellschaft, 1908, 41,2233-43). Examples include compounds that have at least two functionalgroups that are capable of reacting with an isocyanate group. Suchfunctional groups include hydroxyl, amino and thiol groups. Examples ofpolyfunctional alcohols useful as linking agents include:polyoxyalkylenes having 2, 3 or 4 carbon atoms in the oxyalkylene groupand having two or more hydroxyl groups, for instance, polyether diolssuch as polyethylene glycol, polyethylene glycol-polypropylene glycolcopolymers, and polytetramethylene glycol; polyester diols, forinstance, the polyester diols derived from polymerization of adipicacid, or other aliphatic diacids, and organic aliphatic diols having 2to 30 carbon atoms; non-polymeric polyols including alkylene glycols andpolyhydroxyalkanes including 1,2-ethanediol, 1,2-propanol diol,3-chloro-1,2-propanediol, 1,3-propanediol, 1,3-butanediol,1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-, 1,5-, and1,6-hexanediol, 2-ethyl-1,6-hexanediol, 1,8-octanediol, 1,10-decanediol,glycerine, trimethylolethane, trimethylolpropane,2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 1,2,6-hexanetriol, andpentaerythritol.

Preferred polyfunctional amines useful as linking agents include: amineterminated polyethers such as, for example, JEFFAMINE D400, JEFFAMINEED, and JEFFAMINE EDR-148, all from Huntsman Chemical Company, Salt LakeCity, Utah; aliphatic and cycloaliphatic amines including amino ethylpiperazine, 2-methyl piperazine, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, 1,4-diaminocyclohexane,1,5-diamino-3-methylpentane, isophorone diamine, ethylene diamine,diethylene triamine, triethylene tetraamine, triethylene pentamine,ethanol amine, lysine in any of its stereoisomeric forms and saltsthereof, hexane diamine, and hydrazine piperazine; and arylaliphaticamines such as xylylenediamine and a,a,a′,a′-tetramethylxylylenediamine.

Mono- and di-alkanolamines that can be used as linking agents include:monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine,and the like.

The fluoropolymers of the present invention are prepared in a suitabledry organic solvent free of groups that react with isocyanate groups.Ketones are the preferred solvents, and methylisobutylketone (MIBK) isparticularly preferred for convenience and availability. The reaction ofthe alcohols with the polyisocyanate is optionally carried out in thepresence of a catalyst, such as dibutyltindilaurate or tetraisopropyltitanate, typically in an amount of from about 0.01 to about 1.0 weight%. A preferred catalyst is tetraisopropyl titanate.

The resulting composition is then diluted with water, or furtherdispersed or dissolved in a solvent selected from the groups comprisingsimple alcohols and ketones that are suitable as the solvent for finalapplication to substrates, hereinafter the “application solvent”.

Alternatively, an aqueous dispersion, made by conventional methods withsurfactants, is prepared by removing solvents by evaporation and the useof emulsification or homogenization procedures known to those skilled inthe art. Surfactants may include anionic, cationic, nonionic, or blends.Such solvent-free emulsions are preferred to minimize flammability andvolatile organic compounds (VOC) concerns.

The final product for application to a substrate is a dispersion (ifwater based) or a solution (if solvents other than water are used) ofthe fluoropolymer.

Preferred polymers of the invention are wherein R_(f) has 4 to 6 carbonatoms, x is 2, y and z are each 1, m is 1 or 2, and r is 0. Otherpreferred embodiments are polymers wherein said fluorinated compoundreacts with about 5 mol % to about 90 mol %, and more preferably about10 mol % to about 70 mol %, of said isocyanate groups. Other preferredembodiments are polymers wherein the linking group is a diamine orpolyamine.

It will be apparent to one skilled in the art that many changes to anyor all of the above procedures may also be used to optimize the reactionconditions for obtaining maximum yield, productivity or product quality.

The present invention further comprises a method of providing waterrepellency, oil repellency, soil resistance, hydrophilic stain release,and wicking to a substrate comprising contacting the polymers of theinvention as solutions or dispersions with a substrate. Suitablesubstrates include fibrous or hard surface substrates as defined below.

The polymers of the invention, as solutions or dispersions, are appliedto the substrate surface by any suitable method. Such methods are wellknown to those skilled in the art, and include, for example, applicationby exhaustion, foam, flex-nip, nip, pad, kiss-roll, beck, skein, winch,liquid injection, overflow flood, roll, brush, roller, spray, dipping,immersion, and the like. It can also be applied by use of theconventional beck dyeing procedure, continuous dyeing procedure orthread-line application.

The dispersion or solution is diluted for application until the percenttotal fluorine in the dispersion or solution, based on weight of thedispersion or solution, is from about 0.01% to about 20%, preferablyfrom about 0.01% to about 15%, and most preferably from about 0.01% toabout 10% by weight. Application rates for the solution or dispersion ofthe present invention are in the range of from about 0.5 to about 1000g/m² depending on the substrate porosity.

The composition of this invention is applied to the substrate as such,or in combination with other finishes or surface treating agents. Thecomposition of the present invention optionally further comprisesadditional components such as treating agents or finishes to achieveadditional surface effects, or additives commonly used with such agentsor finishes. Such additional components comprise compounds orcompositions that provide surface effects such as no iron, easy to iron,shrinkage control, wrinkle free, permanent press, moisture control,softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stainrepellency, stain release, soil resistance, soil release, waterrepellency, oil repellency, odor control, antimicrobial, stain resist,sun protection, and similar effects. One or more such treating agents orfinishes can be combined with the blended composition and applied to thefibrous substrate.

In particular for fibrous substrates, when textiles such as synthetic orcotton fabrics are treated, a wetting agent can be used, such as ALKANOL6112 available from E. I. du Pont de Nemours and Company, Wilmington,Del. When cotton or cotton-blended fabrics are treated, awrinkle-resistant resin can be used such as PERMAFRESH EPC availablefrom Omnova Solutions, Chester, S.C.

Other additives commonly used with such treating agents or finishes canalso be present such as surfactants, pH adjusters, cross linkers,wetting agents, wax extenders, and other additives known by thoseskilled in the art. Suitable surfactants include anionic, cationic,nonionic, and combinations thereof. For instance, a suitable anionicsurfactant is sodium alkyl sulfate, available as SUPRALATE WAQE fromWitco Corporation, Greenwich Conn. Examples of such finishes or agentsinclude processing aids, foaming agents, lubricants, anti-stains, andthe like. The composition is applied at a manufacturing facility,retailer location, or prior to installation and use, or at a consumerlocation.

Optionally a blocked isocyanate to further promote durability can beadded to the fluoropolymer of the present invention (i.e., as a blendedisocyanate). An example of a suitable blocked isocyanate is HYDROPHOBALHYDORPHOBOL XAN available from Ciba Specialty Chemicals, High Point N.J.Other commercially available blocked isocyanates are also suitable foruse herein. The desirability of adding a blocked isocyanate depends onthe particular application for the treating agent. For most of thepresently envisioned applications, it does not need to be present toachieve satisfactory cross-linking between chains or bonding to thesubstrate. When added as a blended isocyanate, amounts up to about 20%by weight can be added.

Optionally, non-fluorinated extender compositions can also be includedin the application composition to obtain some combination of benefits.Examples of such an optional additional extender polymer composition isthat disclosed in co-pending U.S. Provisional Application 60/607,612filed Sep. 7, 2004 (CH-2996), and in U.S. Ser. No. 11/175680 filed Jul.6, 2005 (CH-3048).

The polymers of the present invention are applied to suitable substratesby a variety of customary procedures. For application to washableapparel fabrics, the polymers are applied, for example, from an aqueousdispersion or an organic solvent solution by brushing, dipping,spraying, padding, roll-coating, foaming or the like. They can beapplied to dyed and undyed textile substrates. For textiles, thecomposition of the present invention is preferably applied in an amountof from about 5 g/L to about 100 g/L, more preferably from about 10 g/Lto about 50 g/L.

In the case of a carpet substrate, the “wet pick up” is the weight ofthe dispersion or solution of the polymer applied to the carpet, basedon the dry weight of the carpet face fiber. A low wet pickup bath systemcan be interchanged with low wet pickup spray or foam systems, and ahigh wet pickup bath system can be interchanged with other high wetpickup systems, e.g., flex-nip system, foam, pad, or flood. The methodemployed determines the appropriate wet pickup and whether theapplication is made from one side of the carpet (spray and foamapplications) or both sides (flex-nip and pad). The following Table 2provides typical process specifications for application to carpetsubstrates.

TABLE 2 Typical Wet Pickup Range for Various Applications ApplicationWet Pickup Range - % Flex-nip 150-350 Flood 100-500 Foam  5-300 Pad100-500 Spray  5-300

The dispersion or solution of the composition of the present inventionis diluted for application. For carpets the percent total fluorine inthe dispersion or solution by weight is preferably from about 0.01% toabout 20%, more preferably from about 0.01% to about 5%, and morepreferably from about 0.01% to about 2%.

Many variations of the conditions for spray, foam, flex-nip, flood, andpad applications are known to those skilled in the art and the precedingconditions are provided as examples and are not intended to beexclusive. The dispersion or solution of the present invention istypically applied to a carpet at a wet pickup of about 5% to about 500%,and preferably cured at from about 220° F. (104° C.) to about 260 (127°C.). Alternatively, the treated carpet can be air dried. Optionally thecarpet can be pre-wetted before application of the dispersion orsolution of the present invention. To pre-wet the carpet, the carpet isimmersed in water and the excess water suctioned off. The “wet pickup”is the weight of the dispersion or solution of the present inventionapplied to the carpet based on the dry weight of the carpet face fiber.

For fibrous substrates, the amount of polymer applied is an amountsufficient to provide at least 100 micrograms per gram to about 5000micrograms per gram by weight of fluorine based on the weight of drysubstrate. For carpets after drying, the treated carpet preferablycontains about 100 micrograms per gram to about 1000 micrograms per gramfluorine based on the weight of the dried carpet.

For leather substrates, the composition of the present invention isapplied by spraying onto dry or semi-wet hides, or immersion of leatherinto the fluoropolymer. The fluoropolymer is applied during processing,or applied after completion of the normal tanning, retanning, or dyingprocesses. It is preferred to combine the application of the polymerwith the manufacturing process during the final stages of leathermanufacture. The amount of polymer applied to the leather is an amountsufficient to provide a dry leather containing from about 0.2 to about20 g fluorine/m², preferably from about 0.2 to about 2.3 g fluorine/m².

The present invention also comprises substrates treated with thecomposition of the present invention. Suitable substrates includefibrous substrates. The fibrous substrates include woven and nonwovenfibers, yarns, fabrics, fabric blends, paper, leather, rugs and carpets.These are made from natural or synthetic fibers including cotton,cellulose, wool, silk, polyamide, polyester, polyolefin,polyacrylonitrile, polypropylene, rayon, nylon, aramid, and acetate. By“fabric blends” is meant fabric made of two or more types of fibers.Typically, these blends are a combination of at least one natural fiberand at least one synthetic fiber, but also can include a blend of two ormore natural fibers or of two or more synthetic fibers. Carpetsubstrates can be dyed, pigmented, printed, or undyed. Fibers and yarnsin the carpet substrates may be dyed, pigmented, printed, or undyed.Carpet substrates can be scoured or unscoured. Substrates to which it isparticularly advantageous to apply the compounds of the presentinvention so as to impart soil resistant properties include thoseprepared from polyamide fibers (such as nylon), cotton and blends ofpolyester and cotton, particularly such substrates being used intablecloths, washable uniforms and the like.

The compositions of the present invention are useful to provide one ormore of excellent water repellency, oil repellency, soil resistance,hydrophilic stain release, and wicking to treated substrates. Theseproperties are obtained using lower fluorine concentrations comparedwith conventional perfluorocarbon surface treatment agents, providingimproved “fluorine efficiency” in the protection of treated surfaces.The compositions of the present invention also allow for the use ofcompounds having minimal environmental impact. The following examplesare intended only to illustrate the invention, and should not beinterpreted so as to limit the invention in any way other than by theattached claims.

Materials and Test Methods

The following test methods and materials were use in the examplesherein.

Test Method 1—Water Repellency

The water repellency of a treated substrate was measured according toMTCC standard Test Method No. 193-2004 and the DuPont TechnicalLaboratory Method as outlined in the TEFLON Global Specifications andQuality Control Tests information packet. The test determines theresistance of a treated substrate to wetting by aqueous liquids. Dropsof water-alcohol mixtures of varying surface tensions are placed on thesubstrate and the extent of surface wetting is determined visually. Thehigher the water repellency rating, the better the resistance of afinished substrate to staining by water-based substances. Thecomposition of water repellency test liquids is shown in Table 3.

TABLE 3 Water Repellency Test Liquids Water Composition, Vol. %Repellency Rating Number Isopropyl Alcohol Distilled Water 1 2 98 2 5 953 10 90 4 20 80 5 30 70 6 40 60 7 50 50 8 60 40 9 70 30 10 80 20 11 9010 12 100 0

Testing procedure: Three drops of Test Liquid 1 are placed on thetreated substrate. After 10 seconds, the drops are removed by usingvacuum aspiration. If no liquid penetration or partial absorption(appearance of a darker wet patch on the substrate) is observed, thetest is repeated with Test Liquid 2. The test is repeated with TestLiquid 3 and progressively higher Test Liquid numbers until liquidpenetration (appearance of a darker wet patch on the substrate) isobserved. The test result is the highest Test Liquid number that doesnot penetrate into the substrate. Higher scores indicate greaterrepellency.

Test Method 2—Oil Repellency

The treated samples were tested for oil repellency by a modification ofMTCC standard Test Method No. 118, conducted as follows. A substratetreated with an aqueous dispersion of polymer as previously described,is conditioned for a minimum of 2 hours at 23° C. and 20% relativehumidity and 65° C. and 10% relative humidity. A series of organicliquids, identified below in Table 4, are then applied dropwise to thesamples. Beginning with the lowest numbered test liquid (RepellencyRating No. 1), one drop (approximately 5 mm in diameter or 0.05 mLvolume) is placed on each of three locations at least 5 mm apart. Thedrops are observed for 30 seconds. If, at the end of this period, two ofthe three drops are still spherical in shape with no wicking around thedrops, three drops of the next highest numbered liquid are placed onadjacent sites and similarly observed for 30 seconds. The procedure iscontinued until one of the test liquids results in two of the threedrops failing to remain spherical to hemispherical, or wetting orwicking occurs.

The oil repellency rating is the highest numbered test liquid for whichtwo of the three drops remained spherical to hemispherical, with nowicking for 30 seconds. In general, treated samples with a rating of 5or more are considered good to excellent; samples having a rating of oneor greater can be used in certain applications.

TABLE 4 Oil Repellency Test Liquids Oil Repellency Rating Number TestSolution 1 NUJOL Purified Mineral Oil 2 65/35 NUJOL/n-hexadecane (v/v)at 21° C. 3. n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane 7n-octane 8 n-heptane

Note: NUJOL is a trademark of Plough, Inc., for a mineral oil having aSaybolt viscosity of 360/390 at 38° C. and a specific gravity of0.880/0.900 at 15° C.

Test Method 3—Accelerated Soiling Drum Test

A drum mill (on rollers) was used to tumble synthetic soil onto carpetsamples. Synthetic soil was prepared as described in AATCC Test Method123-2000, Section 8. Soil-coated beads were prepared as follows.Synthetic soil, 3 g, and 1 liter of clean nylon resin beads [SURLYNionomer resin beads, ⅛- 3/16 inch (0.32-0.48 cm) diameter, were placedinto a clean, empty canister. SURLYN is an ethylene/methacrylic acidcopolymer, available from E. I. du Pont de Nemours and Co., Wilmington,Del. The canister lid was closed and sealed with duct tape and thecanister rotated on rollers for 5 min. The soil-coated beads wereremoved from the canister.

Carpet samples to insert into the drum were prepared as follows. Totalcarpet sample size was 8×25 inch (20.3×63.5 cm) for these tests. Thecarpet pile of all samples was laid in the same direction. The shorterside of each carpet sample was cut in the machine direction (with thetuft rows). Strong adhesive tape was placed on the backside of thecarpet pieces to hold them together. The carpet samples were placed inthe clean, empty drum mill with the tufts facing toward the center ofthe drum. The carpet was held in place in the drum mill with rigidwires. Soil-coated resin beads, 250 cc, and 250 cc of ball bearings (5/16 inch, 0.79 cm diameter) were placed into the drum mill. The drummill lid was closed and sealed with duct tape. The drum was run on therollers for 2-½ min at 105 revolutions per minute (rpm). The rollerswere stopped and the direction of the drum mill reversed. The drum wasrun on the rollers for an additional 2-½ minutes at 105 rpm. The carpetsamples were removed and vacuumed uniformly to removes excess dirt. Thesoil-coated beads were discarded.

The Delta E color difference for the soiled carpet was measured for thetest and control items versus the original unsoiled carpet. Colormeasurement of each carpet was conducted on the carpet following theaccelerated soiling test. For each control and test sample the color ofthe carpet was measured, the sample was soiled, and the color of thesoiled carpet was measured. The Delta E is the difference between thecolor of the soiled and unsoiled samples, expressed as a positivenumber. The color difference was measured on each item, using a MinoltaChroma Meter CR-410. Color readings were taken at five different areason the carpet sample, and the average Delta E was recorded. The controlcarpet for each test item was of the same color and construction as thetest item. A lower Delta E indicates less soiling and superior soilresistance.

Test Method 4—Wicking Test

For the wicking test, 5 drops of DI water were placed on the cottonsamples on different areas of the material. The time (in seconds) ittook to completely absorb into the cotton was recorded. Wicking is anindication of hydrophilicity, and test results are referred to hereineither wicking or hydrophilic stain release. For garments whererepellency is important, a higher wicking number is desired.

Test Method 5—Stain Release Evaluation

The stain release test was taken from the MTCC Test Method 130-1995.Five drops of either mineral oil or corn oil were placed in the centerof the treated cotton sample on a piece of blotter paper. A piece ofglassine paper (weighing paper) was placed over the spot and afive-pound weight was placed on top of the paper. After 60 seconds, theweight and glassine paper were removed. Four red dots were marked aroundthe oil spot. The cotton material were placed in the Kenmore washingmachine with the following settings of Large load, Warm (100° F.)/Cold,One rinse, Ultra Clean (setting 12), and Normal (fast/slow). Then 100 gof MTCC WOB detergent and 4 lbs. of material including ballasts wereadded to the washing machine. After washing, the samples were placed inthe Kenmore dryer on the high setting for 45 minutes. The samples wererated based on the Stain Release Replica.

TABLE 5 Stain Release Grades Grade 5 Stain equivalent to Standard Stain5 Grade 4 Stain equivalent to Standard Stain 4 Grade 3 Stain equivalentto Standard Stain 3 Grade 2 Stain equivalent to Standard Stain 2 Grade 1Stain equivalent to Standard Stain 1

Grade 5 represents the best stain removal and Grade 1 the poorest stainremoval.

Test Method 6—Wash Durability

The fabric samples were washed following the washing procedure ofInternational Standard for textile testing. Fabric samples are loadedinto a horizontal drum, front-loading type (Type A, WASCATORFom71MP-Lab) of automatic washing machine with a ballast load to give atotal dry load of 4 lb. A commercial detergent is added (AATCC 1993standard Reference Detergent WOB) and the washer programmed with highwater level with warm water (105° F., 41° C.), 15 minutes normal washcycle followed by 2 times 13 minutes rinse and then 2 minutes spin dry.The sample and ballast are washed a designated number of times (5HW for5 washes, 20HW for 20 washes, etc.). After washing, the samples wereplaced in a Kenmore dryer on the high setting for 45 minutes. Thesamples are then again tested for stain release and wicking using TestMethods 4 and 5 to indicate durability of these properties.

Materials A) Carpet

1) Residential

A residential carpet was used for testing in the Examples whichconsisted of a residential loop carpet construction (30 oz/sq yd) havinga nylon 6,6 face fiber that had been dyed to a light yellow color andhad received a stain resist treatment of 1.2% of stain resist SR-500available from E. I. du Pont de Nemours and Company, Wilmington, Del.(100% solids basis).

2) Commercial

The commercial carpet used for testing of Examples 1 and 2 consisted ofa commercial loop carpet construction (28 oz/sq yd) having a nylon 6,6face fiber that had been dyed to a yellow color. Carpet was obtainedfrom Invista, Inc., Wilmington, Del.

The residential and commercial carpets for testing received a pre-sprayapplication of water at 25% wet pickup. The carpets were then treatedwith spray application of the fluoropolymers of the Examples andComparative Examples at 25% wet pick-up. The dispersions were dilutedwith water to the degree necessary to obtain a desired fluorine content(as indicated in the Tables in the Examples) delivered to the carpetusing 25% wet pick-up. The treated carpet was then dried to a carpetfiber face temperature of 250° F. (121° C.).

B) Textile

100% Avondale cotton (white woven cotton available from Avondale Mills,Warrenville, S.C.) was used for testing in the Examples. The dispersedfluoropolymers of the Examples each were added to a separate 200 gaqueous bath in the amount indicated in the Tables in the Examples. Thecotton was then run through the bath for a pad application of thefluoropolymer, and then through the padder. The cotton was then cured at330° F. (166° C.) for 3 minutes, and permitted to cool to ambienttemperature.

EXAMPLES Example 1

A 400 mL shaker tube was charged with perfluoroethylethyl iodide (PFEEI)(45 g) and VAZO 64 (1 g), a polymerization initiator available from E.I. du Pont de Nemours and Company, Wilmington, Del. After coolevacuation, ethylene (6 g) and tetrafluoroethylene (25 g) were added.The resulting mixture was heated to 80° C. for 20 hours. The unreactedperfluoroethylethyl iodide was recovered by vacuum distillation at roomtemperature. The remaining solid was extracted with CH₃CN (3×100 mL).The CH₃CN extracts were concentrated and distilled at reduced pressureto give pure iodide 1,1,2,2,5,5,6,6-octahydroperfluoro-1-iodooctane. Thesolid remaining after CH₃CN extraction was extracted with warmtetrahydrofuran. The tetrahydrofuran extract was concentrated and driedto give pure1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-iodododecane. The solidremaining after tetrahydrofuran extraction was mainly iodides of formulaC₂F₅(CH₂CH₂CF₂CF₂)_(n)CH₂CH₂I (wherein n=3 and higher oligomers), whichhave very low solubility in common solvents. The products1,1,2,2,5,5,6,6-octahydroperfluoro-1-iodooctane and1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-iodododecane werecharacterized by H NMR and F NMR as shown below:

A) 1,1,2,2,5,5,6,6-octahydroperfluoro-1-iodooctane: mp 75-77° C.:

-   H NMR (CDCl3) 2.33 (m, 4H), 2.68 (m, 2H), 3.24 (m, 2H) ppm.-   F NMR (CDCl3) −85.9 (s, 3F), −115.8 (m, 4F), −119.2 (m, 2F) ppm.

B) 1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-iodododecane: mp125-8° C.:

-   H NMR (acetone-d6) 2.46 (m, 8H), 2.77 (m, 2H), 3.37 (m, 2H) ppm.-   F NMR (acetone-d6) −86.7 (s, 3F), −117.1 (m, 6F), −117.3 (m, 2F),    −119.5 (m, 2F) ppm.

A mixture of 1,1,2,2,5,5,6,6-octahydroperfluoro-1-iodooctane (136.91 g,248.88 mmol) prepared as above, and N-methylformamide (NMF) (273 mL) washeated to 150° C. for 19 hours. The reaction mixture was washed withwater (4×500 mL) to give a residue. A mixture of this residue, ethanol(200 mL), and concentrated hydrochloric acid (1 mL) was gently refluxed(85° C. bath temperature) for 2.5 hours. The reaction mixture was washedwith water (200 mL×2), diluted with dichloromethane (200 mL), dried oversodium sulfate overnight. The dichloromethane solution was concentratedand distilled at reduced pressure to give1,1,2,2,5,5,6,6-octahydroperfluoro-1-octanol, 50.8 g.

To a dry 250 ml flask was charged with DESMODUR N3300 isocyanate (5 g,available from Bayer Company, Pittsburgh, Pa.). The flask was set upwith reflux condenser, thermal couple under nitrogen gas. This wasfollowed by addition of 1,1,2,2,5,5,6,6-octahydroperfluoro-1-octanol(5.7 g) and MIBK (methyl isobutyl ketone) (20 g). The mixture was heatedto 50° C. Dibutyltin dilaurate in MIBK (0.4% solution, 2.4 g) was added.The reaction temperature was adjusted to 85° C. and was held for 4hours. Water (6 g) was added slowly over time and the mixture held at75° C. for 8 hrs. Testing with an isocynate test strip (AliphaticIsocyanate Surface SWYPE, Colormetric Technologies, Inc, Des Plaines,Ill.) showed no more isocyanate was present. Witco C-6094 (1.57 gavailable from Akzo Nobel Surface Chemistry, LLC, Houston, Tex.) wasmixed with hot deionized water (30 g) and added to the reaction mixture.The reaction mixture was stirred at 75° C. for about 2 hours, thensonified for 2 minutes. The MIBK was removed by vacuum distillation andthe dispersion was filtered through a milk filter. The percent solidswas adjusted by adding deionized water to 24%. The resultingfluoropolymer was applied to commercial carpet as described previouslyunder Materials. The carpet was tested for water repellency using TestMethod 1, oil repellency using Test Method 2, and accelerated soilresistance using Test Method 3, with results shown below in Table 6.

Comparative Example A

Comparative Example A was a commercially available carpet productavailable from E. I. du Pont de Nemours and Company, Wilmington, Del.The fluoropolymer was prepared from R_(f)CH₂CH₂OH wherein R_(f) is amixture of perfluoroalkyl homologs containing from 2 to 18 carbon atoms,and DESMODUR N100 isocyanate. The fluoropolymer was applied to carpetand tested as in Examples 1 and 2. The results are shown in Tables 6 and7 respectively.

TABLE 6 Commercial Carpet Repellency Sample F ppm* Water Oil After Drumsoil ΔE Comparative example A 800 6 5 35.87 Example 1 500 5 3 34.16Example 1 800 5 4 33.31 *ppm = micrograms per gram

The data in Table 6 shows that Example 1 had better soil resistancecompared with Comparative Example A at the same fluorine level, and alsoat a lower fluorine level. Oil and water repellency were comparable tothat of Comparative Example A at the same fluorine level.

Example 2

A mixture of1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-iodododecane (65.62 g)prepared as in Example 1, and N-methylformamide (135 mL) was heated to150° C. for 4 hours. The reaction mixture was washed with water (1 L) togive a solid product. This solid product was added ethanol (150 mL) andconcentrated hydrochloric acid (1 mL) to the solids and heated at reflux(85° C.) for 19 hours. The reaction mixture was poured into water (500mL) and the resulting solid was washed with water (3×300 mL), dried onvacuum to give1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-dodecanol (50.8 g),yield 98%, mp 112-5° C.

To a dry 250 ml flask was charged with DESMODUR N3300 isocyanate (2.0 gavailable from Bayer Company, Pittsburgh, Pa.). The flask was set upwith reflux condenser, thermal couple under nitrogen gas. This wasfollowed by addition of cyclohexanol (0.26 g from Aldrich Company, St.Louis, Mo.), 1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-dodecanol(3.15 g) prepared as described above, and MIBK (methyl isobutylketone)(30 g). The mixture was heated to 50° C. Dibutyltin dilaurate in MIBK(0.4% solution, 2 g) was added. The reaction temperature was adjusted to85° C. and was held for 4 hours. Testing with an isocynate test strip(Aliphatic Isocyanate Surface SWYPE, Colormetric Technologies, Inc, DesPlaines, Ill.) showed no more isocyanate was present. Witco C-6094 (1.17g) (available from Akzo Nobel Surface Chemistry, LLC, Houston, Tex.) wasmixed with hot deionized water (60 g) and added to the reaction mixture.55 g of hot toluene were added. The reaction mixture was stirred at 70°C. for about an hour, then sonified four minutes. No final reaction withwater was conducted. Solvents were removed by vacuum distillation andthe product was filtered through a milk filter. A dispersion wasobtained with 10.4% in solids. The resulting fluoropolymer was appliedto commercial carpet as described previously under Materials. The carpetwas tested for water repellency using Test Method 1, oil repellencyusing Test Method 2, and accelerated soil resistance using Test Method3. The resulting data is in Table 7.

TABLE 7 Commercial Carpet Repellency Sample F ppm Water Oil After Drumsoil ΔE Comparative Example A 800 6 5 35.27 Example 2 330 5 0 35.64 *ppm = micrograms per gram

The data in Table 7 demonstrated that Example 2 had comparable soilresistance when compared to the Comparative Example A while containing amuch lower fluorine level. Water repellency remained similar while oilrepellency did not. It is not unusual to have low oil repellency whenfluorine level is very low (about 300 ppm) on carpet.

Comparative Example B

A 4-neck 1 mL round bottom flask was set-up with an additional funnel,thermocouple, mechanical stirrer, a nitrogen inlet, condenser, and gasoutlet. The flask was charged with DESMODUR N3300 isocyanate (156.9 g)available from Bayer Company, Pittsburgh, Pa., MIBK (methylisobutylketone) (92 g), and FeCl₃ in MIBK (0.4% solution, 2.8 g). Thereaction mixture was heated to 60° C. Poly(ethylene glycol) methyl ether(MPEG750, 16.45 g, available from Aldrich Company, St. Louis, Mo.) wasadded dropwise through a dropping funnel. The reaction mixture washeated at 60° C. for 30 minutes, followed by addition of 1H, 1H, 2H, 2Hperfluorooctanol available from E. I. du Pont de Nemours and Company,Wilmington, Del. (120 g) through a dropping funnel. The reactiontemperature was raised to 95° C. and was held for 4 hrs. The temperaturewas dropped to 85° C., and then 115 g of MIBK was added to the solutionfollowed by 46 g of water, and heated at 85° C. overnight. When testingfor isocyanates using a test strip (Aliphatic Isocyanate Surface SWYPE,Colormetric Technologies, Inc, Des Plaines, Ill.) was negative, thesolution was cooled to 75° C. 1000 g of hot water (75-80° C.) was thenadded to the solution without stirring. This was stirred for 30 minutesat 78° C. MIBK was removed by vacuum distillation and the dispersion wasfiltered through a milk filter. Standardization with deionized watergave a dispersion with 25% solid content. The resulting fluoropolymerwas applied to 100% white Avondale cotton from Avondale Mills,Warrenville, S.C. as described previously under Materials using aloading level of 0.3% fluorine by weight of the bath. The fabric wastested for wicking and hydrophilic stain release using Test Methods 4,5, and 6. The results are in Tables 8 and 9.

Comparative Example C

Comparative Example C was a commercially available textile treatingagent available from E. I. du Pont de Nemours and Company, Wilmington,Del. The fluoropolymer was prepared from R_(f)CH₂CH₂OH wherein R_(f) isa mixture of perfluoroalkyl homologs containing from 2 to 18 carbonatoms, poly(ethylene glycol) methyl ether (MPEG750, available fromAldrich Company, St. Louis, Mo.), and DESMODUR N100 isocyanate availablefrom Bayer Company, Pittsburgh, Pa. The fluoropolymer was applied towhite 100% Avondale cotton from Avondale Mills, Warrenville, S.C. asdescribed previously under Materials using a loading level of 0.3%fluorine by weight of the bath. The fabric was tested for wicking andhydrophilic stain release using Test Methods 4, 5, and 6. The resultsare in Tables 8 and 9.

Example 3

To a dry 250 ml flask was charged with DESMODUR N3300 isocyanate (3.5 g,available from Bayer Company, Pittsburgh, Pa.). The flask was then setup with reflux condenser, thermal couple under nitrogen. This wasfollowed by addition of 1,1,2,2,5,5,6,6-octahydroperfluoro-1-octanol(3.18 g) prepared as in Example 1, poly(ethylene glycol) methyl ether(MPEG750, 3.5 g, available from Aldrich Company, St. Louis, Mo.), andMIBK (methyl isobutyl ketone) (26 g). Dibutyltin dilaurate in MIBK (0.4%solution, 0.8 g) was added. The reaction temperature was adjusted to 85°C. and was held for about 3 hrs. Hot deionized water (63 g) was addedand the mixture held at 85° C. for 1 hr. The mixture was sonified for 2minutes. MIBK was removed by vacuum distillation and the mixture wasfiltered through a milk filter. A dispersion was obtained (solids17.9%). The resulting fluoropolymer was applied to fabric (Avondale 100%white cotton, available from Avondale Mills, Warrenville, S.C.) asdescribed previously under Materials using a loading level of 0.3%fluorine by weight of the bath. The fabric was tested for wicking andhydrophilic stain release using Test Methods 4, 5, and 6. The resultsare in Table 8.

TABLE 8 Fabric Avondale cotton Avondale cotton Avondale cotton ExampleComparative C Comparative B Example 3 Bath Composition, 200 g totalFluoropolymer, grams 6 (8.04% F) 9.61 (5.02% F) 17.05 (2.83% F) Aceticacid, g 0.5 0.5 0.5 Permafresh, g 14 14 14 Water, g 179.5 175.89 168.45Application to Fabric Dry weight, g* 95.5 94.2 96.9 Wet weight, g* 124119.6 124 Leader weight, g* 21 21.85 23 Wet pickup % 66.44 65.31 67.79Stain Release Ratings Corn Oil rating 0 HW 4 4 3 5 HW 3.5 3.5 3 Mineraloil rating 0 HW 3 4 3 5 HW 2.5 3.5 2 Wicking time, sec 0HW >180 >180 >180 5 HW 9-20 48->180 20->180 *Leader weight is the weightof the fabric that was not wetted and thus not padded. Dry weight meansthe weight of fabric when it was dry. Wet weight means the weight of thefabric after it was padded and after the leader part was cut off.

The data in Table 8 shows that the stain release of Example 3 wascomparable to that of Comparative Examples B and C while having a lowerfluorine level present. Wicking time was also similar. The drop inwicking time after five washes is an indication of the level ofdurability of the wicking.

Example 4

A mixture of1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-iodododecane (65.62 g)prepared as in Example 1, and N-methylformamide (135 mL) was heated to150° C. for 4 hours. The reaction mixture was washed with water (1 L) togive a solid product. This solid product was added ethanol (150 mL) andconcentrated hydrochloric acid (1 mL) to the solids and heated at reflux(85° C.) for 19 hours. The reaction mixture was poured into water (500mL) and the resulting solid was washed with water (3×300 mL), dried onvacuum to give1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-dodecanol (50.8 g),yield 98%, mp 112-5° C.

A mixture of1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-iodododecane (65.62 g)prepared as above, and N-methylformamide (135 mL) was heated to 150° C.for 4 hours. The reaction mixture was washed with water (1 L) to give asolid product. This solid product was added ethanol (150 mL) andconcentrated hydrochloric acid (1 mL) to the solids and heated at reflux(85° C.) for 19 hours. The reaction mixture was poured into water (500mL) and the resulting solid was washed with water (3×300 mL), dried onvacuum to give1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-dodecanol (50.8 g),yield 98%, mp 112-5° C.

To a dry 250 ml flask was charged with DESMODUR N3300 isocyanate (3.0 g,available from Bayer Company, Pittsburgh, Pa.). The flask was then setup with reflux condenser, thermal couple under nitrogen gas. This wasfollowed by addition of1,1,2,2,5,5,6,6,9,9,10,10-dodecahydroperfluoro-1-dodecanol (2.54 g)prepared as described above, poly(ethylene glycol) methyl ether(MPEG750, 2.96 g, available from Aldrich Company, St. Louis, Mo.), andmethyl isobutyl ketone (MIBK) (30 g). Dibutyltin dilaurate in MIBK (0.4%solution, 1.6 g) was added. The reaction temperature was adjusted to 85°C. and was held for about 6 hrs. Hot deionized water (47 g) was addedand the mixture held at 75° C. for overnight. MIBK was removed by vacuumdistillation and the mixture was filtered through a milk filter. Adispersion was obtained (solids 16.5%). The resulting fluoropolymer wasapplied to fabric (100% Avondale cotton from Avondale Mills,Warrenville, S.C.) as described previously under Materials using aloading level of 0.3% by weight of the bath. The fabric was tested forwicking and hydrophilic stain release using Test Methods 4, 5, and 6.The results are in Table 9.

TABLE 9 Fabric Avondale cotton Avondale cotton Avondale cotton ExampleComparative C Comparative B Example 4 Bath Composition, 200 g totalFluoropolymer 6 (8.04% F) 9.61 (5.02% F) 16.03 (3.01% F) Acetic acid, g0.5 0.5 0.5 Permafresh, g 14 14 14 Water, g 179.5 175.89 169.47Application to Fabric Dry weight, g* 69.5 66 62.3 Wet weight, g* 88.5 8479.7 Leader weight, g* 15.8 14.83 14.49 Wet pickup % 64.80 64.16 66.71Stain Release Ratings Corn Oil rating 0 HW 4.5 4.5 4 5 HW 4 4 3 Mineraloil rating 0 HW 4.5 4.5 3.8 5 HW 4 4 3 Wicking time, sec 0HW >180 >180 >180 5 HW 9-20 48->180 20->180 (600) *Leader weight is theweight of the fabric that was not wetted and thus not padded. Dry weightmeans the weight of fabric when it was dry. Wet weight means the weightof the fabric after it was padded and after the leader part was cut off.

The data in Table 9 shows that the stain release of Example 4 wascomparable to that of Comparative Examples B and C while having a lowerfluorine level present. Wicking time for Example 4 was higher than theComparative Examples B and C and had comparable durability.

Example 5

To a dry 500 ml flask was charged with DESMODUR N3300 isocyanate (60.0g, available from Bayer Company, Pittsburgh, Pa.). The flask was set upwith reflux condenser, thermal couple under nitrogen gas. This wasfollowed by addition of methyl isobutyl ketone (35.24 g) and dibutyltindilaurate in methyl isobutyl ketone (0.4% solution, 6.0 g). The mixturewas heated to 60° C. 1,1,2,2,5,5,6,6-octahydroperfluoro-1-octanol (84.81g) in methyl isobutyl ketone (109.57 g) was added. The reactiontemperature was adjusted to 100° C. and was held for 72 hours. Water(1.78 g) was added slowly over time and the mixture held at 100° C. for12 hrs. Testing with an isocynate test strip (Aliphatic IsocyanateSurface SWYPE, Colormetric Technologies, Inc, Des Plaines, Ill.) showedno more isocyanate was present. To 20.0 g of the above mixture was addedDOWFAX 2A1(1.6 g available from Dow Chemical Company, Midland, Mich.)mixed with hot deionized water (28.0 g) and added to the reactionmixture. The reaction mixture was stirred at 75° C. for about 2 hours,then sonified for 4 minutes and filtered through a milk filter. Themethyl isobutyl ketone was removed by vacuum distillation and thedispersion was filtered through a milk filter. The percent solids wasadjusted by adding deionized water to 15.57%. The resultingfluoropolymer was applied to commercial carpet as described previouslyunder Materials. The carpet was tested for water repellency using TestMethod 1, oil repellency using Test Method 2, and accelerated soilresistance using Test Method 3, with results shown below in Table 10.

TABLE 10 Commercial Carpet Repellency Sample F ppm* Water Oil After Drumsoil ΔE Comparative Example A 800 6 5 23.79 Example 3 800 5 2 23.84 *ppm= micrograms per gram

The data in Table 10 shows that Example 5 had comparable soil resistanceto that of Comparative Example A at the same fluorine level. Oil andwater repellency were comparable to that of Comparative Example A at thesame fluorine level.

Example 6

To a dry 500 ml flask was charged with DESMODUR N100 isocyanate (60.0 g,available from Bayer Company, Pittsburgh, Pa.). The flask was set upwith reflux condenser, thermal couple under nitrogen gas. This wasfollowed by addition of methyl isobutyl ketone (35.24 g) and dibutyltindilaurate in methyl isobutyl ketone (0.4% solution, 6.0 g). The mixturewas heated to 60° C. 1,1,2,2,5,5,6,6-octahydroperfluoro-1-octanol (85.59g) in methyl isobutyl ketone (110.35 g) was added. The reactiontemperature was adjusted to 100° C. and was held for 72 hours. Water(1.78 g) was added slowly over time and the mixture held at 100° C. for12 hrs. Testing with an isocynate test strip (Aliphatic IsocyanateSurface SWYPE, Colormetric Technologies, Inc, Des Plaines, Ill.) showedno more isocyanate was present. To 20.0 g of the above mixture was addedWITCO C-6094 (1.6 g available from Akzo Nobel Surface Chemistry, LLC,Houston, Tex.) mixed with hot deionized water (28.0 g) and added to thereaction mixture. The reaction mixture was stirred at 75° C. for about 2hours, then sonified for 4 minutes and filtered through a milk filter.The methyl isobutyl ketone was removed by vacuum distillation and thedispersion was filtered through a milk filter. The percent solids wasadjusted by adding deionized water to 15.52%. The resultingfluoropolymer was applied to commercial carpet as described previouslyunder Materials. The carpet was tested for water repellency using TestMethod 1, oil repellency using Test Method 2, and accelerated soilresistance using Test Method 3, with results shown below in Table 11.

TABLE 11 Commercial Carpet Repellency Sample F ppm* Water Oil After Drumsoil ΔE Comparative Example A 800 6 5 35.78 Example 4 800 5 2 34.57 *ppm= micrograms per gram

The data in Table 11 shows that Example 6 had better soil resistancecompared with Comparative Example A at the same fluorine level. Oil andwater repellency were comparable to that of Comparative Example A at thesame fluorine level.

1. A polymer having at least one carbamate linkage prepared by: (i)reacting (a) at least one diisocyanate, polyisocyanate, or mixturethereof, having isocyanate groups, and (b) at least one fluorinatedcompound selected from the formula (I):R_(f)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)(R¹)_(r)—XH   (I) whereinR_(f) is a linear or branched chain perfluoroalkyl group having 1 toabout 6 carbon atoms; subscript x is an integer from 1 to about 6;subscripts y, z and m are each independently 1, 2 or 3, or a mixturethereof; subscript r is 0 or 1; the total number of carbons in saidformula (I) excluding (R¹)_(r)—XH ranges from about 8 to about 22; X is—O—, —NR—, —S—, —S(CH₂)_(t)O—, or —S(CH₂)_(t)NR—; subscript t is from 1to about 10; R is H or C₁₋₄ alkyl; R¹ is a divalent radical selectedfrom the group consisting of —S(CH₂)_(n)—,

n is an integer of 2 to 4; s is an integer of 1 to 50; R², R³, and R⁴are each independently hydrogen or an alkyl group containing 1 to 6carbon atoms; and (ii) optionally reacting with (c) water, a linkingagent, or a mixture thereof.
 2. The polymer of claim 1 wherein for thereactant of formula (I), X is O, and subscripts x, y, z, and m are eachindependently 1 or 2, and subscript r is
 0. 3. The polymer of claim 1wherein R_(f) has 4 to 6 carbon atoms.
 4. The polymer of claim 1 whereinR_(f) has 4 to 6 carbon atoms, x is 2, y and z are each 1, m is 1 or 2,and r is
 0. 5. The polymer of claim 1 wherein said fluorinated compoundreacts with about 5 mol % to about 90 mol % of said isocyanate groups.6. The composition of claim 1 wherein the diioscyanate or polyisocyanateis selected from the group consisting of hexamethylene diisocyanatehomopolymer, 3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate,bis-(4-isocyanatocylohexyl)methane and d iisocyanate trimers of formulas(IIa), (IIb), (IIc) and (IId):


7. The polymer of claim 1 wherein step (i) reacting, further comprises(d) a non-fluorinated organic compound selected from the groupconsisting of formulaR¹⁰—(R¹¹)_(k)—YH wherein R¹⁰ is a C₁-C₁₈ alkyl, a C₁-C₁₈ omega-alkenylradical or a C₁-C₁₈ omega-alkenoyl; R¹¹ is selected from the groupconsisting of

wherein R², R³ and R⁴ are each independently, H or C₁ to C₆ alkyl, and sis an integer of 1 to 50; k is 0 or 1, Y is —O—, —S—, or —NR⁵— in whichR⁵ is H or alkyl containing 1 to 6 carbon atoms.
 8. The polymer of claim7, wherein the compound of formula R¹⁰—(R¹¹)_(k)—YH comprises ahydrophilic water-solvatable material comprising at least onehydroxy-terminated polyether of formula (III):

wherein R is a monovalent hydrocarbon radical containing from about oneto about six aliphatic or alicyclic carbon atoms; m is a positiveinteger, and m1 and m2 are each independently a positive integer orzero; said polyether having a weight average molecular weight up toabout
 2000. 9. The polymer of claim 7 wherein said non-fluorinatedcompound reacts with about 0.1 mol % to about 60 mol % of saidisocyanate groups.
 10. The polymer of claim 1 wherein the linking agentis a diamine or polyamine.
 11. The polymer of claim 1 in the form of anaqueous dispersion or solution.
 12. The polymer of claim 1 furthercomprising one or more agents providing at least one surface effectselected from the group consisting of no iron, easy to iron, shrinkagecontrol, wrinkle free, permanent press, moisture control, softness,strength, anti-slip, anti-static, anti-snag, anti-pill, stainrepellency, stain release, soil resistance, soil release, waterrepellency, oil repellency, stain resist, odor control, antimicrobial,and sun protection.
 13. The polymer of claim 1 further comprising asurfactant, pH adjuster, cross linker, wetting agent, blockedisocyanate, wax extender, or hydrocarbon extender.
 14. A method ofproviding water repellency, oil repellency, soil resistance, hydrophilicstain release, and wicking to substrates comprising contacting saidsubstrate with a polymer having at least one carbamate linkage preparedby: (i) reacting (a) at least one diisocyanate, polyisocyanate, ormixture thereof, having isocyanate groups, and (b) at least onefluorinated compound selected from the formula (I):R_(f)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)(R¹)_(r)—XH   (I) whereinR_(f) is a linear or branched chain perfluoroalkyl group having 1 toabout 6 carbon atoms; subscript x is an integer from 1 to about 6;subscripts y, z and m are each independently 1, 2 or 3, or a mixturethereof; subscript r is 0 or 1; the total number of carbons in saidformula (I) excluding (R¹)_(r)—XH ranges from about 8 to about 22; X is—O—, —NR—, —S—, —S(CH₂)_(t)O—, or —S(CH₂)_(t)NR—; subscript t is from 1to about 10; R is H or C₁₋₄ alkyl; R¹ is a divalent radical selectedfrom the group consisting of —S(CH₂)_(n)—,

n is an integer of 2 to 4; s is an integer of 1 to 50; R², R³, and R⁴are each independently hydrogen or an alkyl group containing 1 to 6carbon atoms; and (ii) optionally reacting with (c) water, a linkingagent, or a mixture thereof.
 15. The method of claim 14 wherein thepolymer is contacted with the substrate as an aqueous dispersion orsolution.
 16. The method of claim 14 wherein the polymer is contactedwith the substrate by means of exhaustion, spray, foam, flex-nip, nip,pad, kiss-roll, beck, skein, winch, liquid injection, overflow flood,brush, roll, spray, dip, roll coating, foaming, or immersion.
 17. Themethod of claim 14 wherein the polymer is contacted with the substratein the presence of an agent providing at least one surface effectselected from the group consisting of no iron, easy to iron, shrinkagecontrol, wrinkle free, permanent press, moisture control, softness,strength, anti-slip, anti-static, anti-snag, anti-pill, stainrepellency, stain release, soil resistance, soil release, waterrepellency, oil repellency, stain resist, odor control, antimicrobial,and sun protection.
 18. A substrate to which has been applied a polymerhaving at least one carbamate linkage prepared by: (i) reacting (a) atleast one diisocyanate, polyisocyanate, or mixture thereof, havingisocyanate groups, and (b) at least one fluorinated compound selectedfrom the formula (I):R_(f)(CH₂)_(x)[(CF₂CF₂)_(y)(CH₂CH₂)_(z)]_(m)(R¹)_(r)—XH   (I) whereinR_(f) is a linear or branched chain perfluoroalkyl group having 1 toabout 6 carbon atoms; subscript x is an integer from 1 to about 6;subscripts y, z and m are each independently 1, 2 or 3, or a mixturethereof; subscript r is 0 or 1; the total number of carbons in saidformula (I) excluding (R¹)_(r)—XH ranges from about 8 to about 22; X is—O—, —NR—, —S—, —S(CH₂)_(t)O—, or —S(CH₂)_(t)NR—; subscript t is from 1to about 10; R is H or C₁₋₄ alkyl; R¹ is a divalent radical selectedfrom the group consisting of —S(CH₂)_(n)—,

n is an integer of 2 to 4; s is an integer of 1 to 50; R², R³, and R⁴are each independently hydrogen or an alkyl group containing 1 to 6carbon atoms; and R_(f) is a linear or branched chain perfluoroalkylgroup having 1 to 6 carbon atoms; and (ii) optionally reacting with (c)water, a linking agent, or a mixture thereof.
 19. The substrate of claim18 wherein, within said fluorinated compound of formula (I), x is 2, yand z are each 1, m is 1 or 2, r is 0, X is —O—, and R_(f) has 6 carbonatoms.
 20. The substrate of claim 18, wherein the diisocyanate orpolyisocyanate is selected from the group consisting of hexamethylenediisocyanate homopolymer; 3-isocyanatomethyl-3,4,4-trimethylcyclohexylisocyanate; bis-(4-isocyanatocylohexyl)methane; and d iisocyanatetrimers of formulas (IIa), (IIb), (IIc) and (IId):


21. The substrate of claim 18 wherein, within said fluorinated compoundof formula (I), when R_(f) has 1 to 4 carbon atoms, said at least oneorganic diisocyanate, polyisocyanate, or mixture thereof, comprisesabout 25 wt % to about 100 wt % of one or more cyclic diisocyanatesselected from the group consisting of 2,4-toluene diisocyanate,2,6-toluene diisocyanate, diphenylmethane 4,4′-diisocyanate,diphenylmethane 2,4′-diisocyanate,3-isocyanatomethyl-3,4,4-trimethylcyclohexyl isocyanate,bis-(4-isocyanatocylohexyl)methane and diisocyanate trimers of formula(IIa), (IIb), (IIc), and (IId):


22. The substrate of claim 18 comprising a fibrous substrate selectedfrom the group consisting of a fiber, yarn, fabric, fabric blend,textile, rug, carpet, paper and leather.
 23. The substrate of claim 18which is selected from the group consisting of polyamide, wool,polyester, polyolefin, polyaramid, acrylic, wool, cotton, jute, sisal,sea grass, coir, and blends thereof.